CN101372464A - Process for preparing low-chlorine isocyanate - Google Patents

Process for preparing low-chlorine isocyanate Download PDF

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Publication number
CN101372464A
CN101372464A CNA2008101611558A CN200810161155A CN101372464A CN 101372464 A CN101372464 A CN 101372464A CN A2008101611558 A CNA2008101611558 A CN A2008101611558A CN 200810161155 A CN200810161155 A CN 200810161155A CN 101372464 A CN101372464 A CN 101372464A
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China
Prior art keywords
phosgene
logistics
reaction
reaction zone
amine reactant
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CNA2008101611558A
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Chinese (zh)
Inventor
H·斯图茨
F·迪尔
A·施瓦茨
R·布伦斯
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Covestro Deutschland AG
Bayer Intellectual Property GmbH
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Bayer MaterialScience AG
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Priority to CN201610868115.1A priority Critical patent/CN107011214A/en
Publication of CN101372464A publication Critical patent/CN101372464A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Abstract

A process for preparing a low chlorine isocyanate comprising providing an amine reactant and reacting the amine reactant with a phosgene stream in a reaction zone to form a product comprising the corresponding isocyanate, wherein the phosgene stream has an average CO content of 0.5 wt% or more.

Description

The method for preparing low-chlorine isocyanates
Background technology
Aliphatic amide or aromatic amine phosgenation prepare isocyanic ester and have special advantage in gas phases.The principle of these methods is established in the art, and as European Patent Publication No EP0289840, its full content is hereby incorporated by, and these methods have begun in industrial enforcement.
WO97/24320 has described a kind of very general passing through makes corresponding (fragrance) amine and phosgene reaction generate the method for isocyanic ester with circulating chlorine gas, phosgene is created on the chlorine from the special special purifying of electrochemical cell in this method, and the excessive carbon monoxide of non-special qualification directly feeds in the phosgenation reactor.Concentration data is not provided at all.Do not provide the secondary component that produces in beginning product or the phosgene or to the explanation of the influence that generates the isocyanic ester quality.Any details of phosgenation processes both was not provided, whether with or carry out without solvent, do not provide yet and carry out the temperature range of isocyanic ester when producing.
Plant-scale phosgenation utilization is usually carried out at the phosgene for preparing in the phosgene producer on the catalyzer by chlorine and carbon monoxide.Before offering phosgenation, the phosgene in the producer at first offers purification step, and wherein it is separated into the logistics of exhaust gas stream photoreactive gas, preferably by the condensation phosgene or by distillation.With the amine real reaction before, the phosgene logistics also mixes with the round-robin phosgene then usually, as disclosed in the International Patent Publication No. WO 2004/037718, its full content is hereby incorporated by.
The phosgene used according to prior art contains the residual CO gas level that is less than 0.05wt% owing to post-processing step.
After the reaction of amine photoreactive gas, the product isocyanic ester carries out purifying by distillation routinely and removes lower boiling and high boiling point by-products produced.Be problematic in many cases, if if the isocyanic ester of purifying has color or modification procedure subsequently such as prepolymerization, allophanamide baseization (biuretization) or trimerizing, for example, be attended by the side reaction of not expecting, it finally has a negative impact to the color of the polyisocyanates of gained again.
This class side reaction is often by the low-down chlorating of concentration or comprise that the compound of the chlorine of hydrolyzable form causes.The compound that removes those hydrolyzable cl contenies that help isocyanic ester (HC compound and HC content) or chloride content is possible in principle, but do not wish to do like this from the angle of producing, because this additional purification step uses by the energy that increases and/or because the loss of yield of heat load has increased production cost.
Summary of the invention
Relate generally to of the present invention prepares the method for isocyanic ester, it is characterized in that the low-level especially randomly compound of the chlorine of hydrolyzable form that comprises.
The invention provides such method, compare, cause having the HC of remarkable minimizing and the product of chloride content, do not have further purification step with the method for prior art.
Surprisingly, have been found that the minimizing of the compound level that helps HC content and chloride content can realize, have 0.5wt% or more carbon monoxide (CO) content if offer the phosgene of amine phosgenation.
The corresponding purposes that provides phosgene to be used for the amine phosgenation of the present invention with 0.5wt% or more CO content.
The present invention further provides and a kind ofly prepare the method for isocyanic ester by corresponding amine and phosgene reaction, randomly in the presence of inert media, the phosgene logistics that wherein offers phosgenation has 0.5wt% or more CO content.
A specific embodiments of the present invention comprises such method, and it comprises: amine reactant is provided; With in reaction zone, make amine reactant and phosgene logistics reaction form the product comprise corresponding isocyanic ester; Wherein the phosgene logistics has 0.5wt% or more CO content.
Embodiment
Singular references used herein " a ", " the " is synonym, and uses interchangeably with " one or more (one or more) " and " at least one (at least a) ", unless other implications clearly represented in language and context.Correspondingly, for example, speak of " a kind of logistics (a stream) ", herein or in additional claim, may refer to single logistics or more than a logistics.
Preferably, the phosgene logistics has the CO content more than 1wt%, more preferably more than 2wt%.But the CO content of phosgene preferably is lower than 8wt%, very preferably is lower than 4wt%.So, in different preferred embodiments, the phosgene logistics has 1-8wt%, 2-8wt%, the average CO content of 1-4wt% and 2-4wt%.
About the regulation of CO content in the phosgene, whether CO offers phosgene separately or whether available from the phosgene production method and to have contained the phosgene logistics of scope CO as described all unimportant as the phosgene source of phosgenation of the present invention.
Preferably, with CO with directly offer phosgenation, and there are not further aftertreatment (working-up) and CO loss available from the mixture of the phosgene of phosgene producer.
The preferred method that phosgene takes place comprise as described in the U.S. Patent Application Publication No. US2006/047170 in the presence of activated-carbon catalyst, in tube bundle reactor, prepare phosgene by chlorine and CO, its full content is hereby incorporated by, wherein have effective cooling, gas temperature is lower than 100 ℃.Another feature of this preferred phosgene generation technology is to reduce pressure water to remove reaction heat by transpiration cooling to occur under the normal atmosphere (absolute pressure) that is lower than 1 crust.Coolant loop is a closed loop, and wherein water is evaporated, and shifts, and in other local condensation, turns back to coolant room for the regeneration evaporation then.This coolant room preferably is contained in the liquid water that all is boiling state any time.CO and chlorine feed logistics are used for preferable methods, and in order to obtain low-level chlorine in phosgene, preferably, the CO molar excess is 2%-20%, more preferably, and 5%-15%.
The phosgene logistics that is used for reacting with amine reactant that offers reaction zone preferably has the HCl content that is less than 15wt%, more preferably, and 0.1-10wt%, most preferably, 2-8wt%.
The method for preparing isocyanic ester of different embodiments preferably finish by a step according to the present invention.This means the mixing of reactant and reaction and form product and occur in the reaction zone.After product left reaction zone, the amino group that is provided and the reaction of phosgene were preferably finished.The special reason that this target value must be made great efforts be because, as not, unreacted amino group can cause the formation of HCl or urea, and it has reduced the isocyanic ester total recovery, and, reduce the service life of reactor and/or the service life of downstream finishing apparatus owing to form precipitation.
The equally preferably operate continuously of the inventive method.
For method of the present invention, can use all to have at least one, preferred 1 to 3, the amino-functional compounds of primary amino group, prerequisite are that they can be converted into the steam form.In this article, whether amine is aliphatic, cyclic aliphatic, araliphatic (araliphatic) or aromatics be actually inessential.
Above-mentioned amino-functional compounds has maximum 22 carbon atoms usually; If 2 or more a plurality of amino group are arranged in the molecule, they are separated by at least 2 carbon atoms each other.
The preferred amine that uses the be converted into gaseous state of the above-mentioned type and do not have obvious (substantial) to decompose.
Be particularly suitable for the diamines of the hydro carbons that is based on aliphatic series or cyclic aliphatic of this purpose with 2 to 18 carbon atoms.
These examples comprise 1,4-diaminobutane, 1,1,8-diamino octane, 1,10-diamino decane, 1,6-diamino-2,4,4-trimethyl cyclohexane and 1,6-diamino-2,2,4-trimethyl cyclohexane, 1-amino-3,3,5-trimethylammonium-5-amino methyl hexanaphthene (IPDA), 2,4-or 2,6-diaminostilbene-methylcyclohexane and 4,4 '-and/or 4,2 '-diamino-dicyclohexyl methane.Preferred especially 1,1-amino-3,3,5-trimethylammonium-5-(amino methyl) hexanaphthene and 4,4 '-and/or 4,2 '-two (aminocyclohexyl) methane.
Being suitable as amine reactant equally is (ring) aliphatic triamine of maximum 22 carbon atoms of having of any needs, and prerequisite is that they are stable under the temperature condition of the inventive method and can be converted into gaseous form.They can be, for example, and triamino hexanaphthene, three (amino methyl) hexanaphthene, triamino methylcyclohexane.What be fit to equally is 1,8-diamino-4-(amino methyl) octane, 1,6,11-undecane triamine, 1,7-diamino-4-(3-amino-propyl group) heptane, 1,6-diamino-3-(amino methyl) hexane or 1,3,5-three (amino methyl) hexanaphthene.
For method of the present invention, the same possible aromatic amine that is to use, it preferably can be converted into gas phase and obviously not decompose.The example of preferred aromatic amine is tolylene diamine (TDA), as 2,4 or 2,6 isomer or its mixture, and diaminobenzene, 2,6-xylidine, naphthylene diamine (NDA) and 2,4 '-or 4,4 '-methylene radical (diphenylamine) are (MDA) or its isomer mixture.Preferred 2,4-and/or 2,6-TDA.
Amine photoreactive gas reactant can also quantitatively provide to reaction chamber with inert media separately.Inert media be included under the temperature of reaction in reaction chamber be gas form and not with the medium that appears at the compound reaction in the reaction process.Inert media mixes with amine and/or phosgene before reaction usually, but also can quantitatively provide from reactant stream separately.For example, may use nitrogen, rare gas element, for example helium or argon gas, perhaps aromatic substance, for example chlorobenzene, dichlorobenzene, dimethylbenzene or carbonic acid gas.The preferred nitrogen and/or chlorobenzene and/or dichlorobenzene of using is as inert media.
Inert media is that 0.001 to 5 amount is used with the ratio of inert media gas volume and amine or phosgene gas volume usually, and is preferred 0.01 to 3, more preferably 0.1 to 1.Preferred inert media enters reaction chamber with amine.
Method of the present invention realizes by this way that preferably amine photoreactive gas reactant and the isocyanic ester that forms at reaction zone are gaseous phases under reaction conditions; In other words, the formation of so preferred eliminating drop.
For above-mentioned reaction conditions is provided, the temperature of reaction zone preferably surpasses 200 ℃, more preferably surpasses 260 ℃, very preferably above 280 ℃.Upper temperature limit preferably is lower than 570 ℃ under this condition, more preferably less than 500 ℃.
Phosgene and amine occur in the reaction of reaction zone separately and surpass 0.1 crust to the absolute pressures less than 20 crust, and preferred 0.5 crust is to 10 crust, and more preferably 0.7 crust is to 5 crust, and very preferably 0.8 crust is to 3 crust.
Pressure to the feeding line of reaction zone is usually above the above-mentioned pressure in the reaction zone self.Pressure in the feeding line is higher than the superior 20-2000 of the choosing millibar of pressure in the reaction zone self, more preferably 30-1000 millibar.
Pressure in the process area on the common stricti jurise after (proper) reaction zone is lower than reaction zone self.Pressure preferably is lower than 10 to 500 millibars of reaction zones, more preferably 30 to 150 millibars.
Reactant is preferably in each case with flow velocity 1-100m/s, more preferably 2 to 50m/s feeds and passes through reaction zone.
The flow velocity of two kinds of reactants in aforementioned region is preferably adjusted so that the average contact time of the amine photoreactive gas reaction mixture that reaction zone obtains is generally 0.01 second to being less than 15 seconds, preferably from surpassing 0.04 second, more preferably from surpassing 0.08 second to being less than 5 seconds to being less than 10 seconds.Average contact time mean from reactant mix beginning up to from reaction chamber, leave enter post-processing step during.Mobile in the inventive method is characterised in that Bodenstein number (Bodenstein number) surpasses 10 in a preferred embodiment, preferably above 100 with more preferably above 250.
It is turbulent that the size of reaction chamber and flow velocity advantageously select to make dominant flowing, promptly, it is a kind of Reynolds number (Reynolds number) at least 2300 that has, preferred at least 2700 flow, for reaction mixture, Reynolds number is formed by the hydraulic diameter (hydraulic diameter) of reaction chamber.
As the result of turbulent flows, obtain the narrow residence time, have and be lower than 10% little standard deviation, preferably be lower than 6%.
Reaction zone does not preferably have movably internals.
Reaction zone comes temperature control through its outside surface.In order to make up productive unit with heavy body, can be with the parallel connection of two or more reactor tubes.Perhaps, reaction can preferably adiabaticly take place.This means the mobile outside surface that does not flow through reaction volume of heating or cooling energy along with technical measures.Preferred reaction is adiabatic to be taken place.
After reaction mixture reacts in reaction zone, behind phosgenation reaction, need to cool off rapidly reactant gases to temperature and be lower than 180 ℃, to avoid owing to the thermal destruction of two/triisocyanate or because sustained reaction, by polymerization, form undesirable by product, because the two/triisocyanate that forms is not heat-staple under 300 to 570 ℃ temperature of reaction.The temperature that is cooled to 100 to 180 ℃ occurs in single-stage or the multistage washer (using the washing tower quenching) that uses inert solvent, as EP-A11403248, and the 2nd hurdle, the 39th row, to the 3rd hurdle, the 18th row is described.
Suitable solvent is hydro carbons preferably, suitably replaced by halogen atom under the situation, for example, chlorobenzene, dichlorobenzene, and toluene.The preferred especially solvent that uses is mono chloro benzene and/or dichlorobenzene.As solvent, can use isocyanic ester or in described solvent prepared isocyanate solution, this solution also can circulate by the heat exchanger that is used to remove energy.In the washing stage, be transferred to washing soln selective isocyanate.(it has kept excessive phosgene from isocyanate-free gas, hydrogenchloride, suitable, inert media is from the solvent of washer) in, reclaim solvent by partial condensation, then reclaim phosgene, for example by the absorption in monochloro benzene and/or dichlorobenzene, and hydrogenchloride, behind purifying under the suitable situation, further use as raw material according to prior art.The spissated isocyanate solution that obtains in quenching and washing tower has the isocyanate concentration of 20wt% at least, preferably 25wt% at least.The spissated isocyanate solution that obtains in quenching and washing tower does not have the hydrogenchloride photoreactive gas of physics (dissolved) and chemical attachment, preferably by rectifying, and further be separated into neat solvent in the distilation steps, low-boiling by-products, pure two-or triisocyanate, and high boiling material (highboilers).The preferred isocyanic ester that uses.
The amount of the compound with hydrolyzable chlorine that can contain by (ring) aliphatic isocyanate that the inventive method obtains preferably is less than 200ppm, more preferably less than 80ppm.
The amount of the compound with hydrolyzable chlorine that the obtainable aromatic isocyanate of the inventive method contains preferably is less than 100ppm, more preferably less than 40ppm.
In the situation of (ring) aliphatic series (isocyanic ester) and the chloride content in the situation of aromatic isocyanate preferably be lower than 800ppm, more preferably less than 500ppm.
The amount w of hydrolyzable chlorine (Cl) in the isocyanic ester in the working range〉detection of 5mg/kg realizes by urethane esterification (urethanization), hydrolysis and Silver Nitrate potentiometric titration, uses associating silver/silver chloride electrode.
In order to detect hydrolyzable cl content, isocyanic ester sample and methanol mixed and urethane esterification refluxed 10 minutes.Then, after the washing, mixture under refluxing by boiling hydrolysis.The ionization chlorine that forms in this process (ionogenic chlorine) carries out acidifying with nitric acid, supplies (made up with) with the sodium-chlor of known quality, then carries out argentometry (argentometric titration) with the Silver Nitrate standardized solution.Titration is supplied with by the reagent metering that increases progressively and is undertaken by the automatic terminal point evaluation (balance titration) under skew control.The consumption of the initial mass of isocyanic ester sample and Silver Nitrate standardized solution is used to calculate hydrolyzable cl content, and considers to supply material.
The obtainable isocyanic ester of the inventive method can be particularly advantageous for producing urethane covering material and tackiness agent and sealing agent and soft and rigid foam.Be these purposes, they are reaction prepolymer at first preferably, uretdione (uretdiones), chlorinated isocyanurates (isocyanurates), iminooxadiazinedionepolyisocyanates diketone (iminooxadiazinediones), biuret or allophanate also can come block (blocked) by own typical method in the document.
The present invention now describes in further detail with following non-limiting examples.
Embodiment
Embodiment 1 (comparative example)
By in slick injection nozzle, mixing, reactant stream A and reactant stream B are supplied to tubular reactor continuously, it has the post-processing stages of the isocyanic ester condensation phase in downstream and distillation isocyanic ester subsequently, reactant stream A is isophorone diamine (isophoronediamine)/noble gas mixtures, reactant stream B is that the amount of introducing is 160% of a theory by phosgene (it the is excessive to reclaim) solution in the evaporation mono chloro benzene with by evaporating the phosgene that obtains from the condensation phosgene in the phosgene generation technology.The gaseous phosgene logistics comprise 2.9wt% hydrogenchloride and the 0.05wt% carbon monoxide.The temperature of two kinds of reactant streams is 300 ℃.The little normal atmosphere that is higher than of pressure in the tubular reactor is at 1300 millibars.
The about 80m/s of the speed of component A in smooth injection nozzle, the speed of B component is about 10m/s before mixing.Because the result of adiabatic reaction state, the temperature in the reactor rises to about 420 ℃.
After leaving reactor, isophorone diisocyanate (IPDI) reaction product is condensed, and with hydrogen chloride by-product, inert substance separates with excessive phosgene, then purifying in distillation process (distillation sequence).The IPDI that obtains has the hydrolyzable cl content of 140ppm and the chloride content of 190ppm.
The IPDI of gained is further processed the formation tripolymer, has the very polyisocyanates of the trifunctional of low-steam pressure, and it is applied to the covering system.In 70% solution in the commercial practices paint solvent, tripolymer is a water clear (water-clear) in fact, has the gloomy chromatic number in Kazakhstan (Hazen colournumber) of 50Apha.
Embodiment 2 (the present invention)
Similarity condition repeats embodiment 1 down, phosgene reaction thing flow B still theoretical 160%, it is 60% that the phosgene solution by vaporization cycle is recycled to degree, the phosgene that reacts required directly provides from phosgene generation technology, with gas form, comprise inert substance and excessive carbon monoxide.Enter the preceding gaseous phosgene logistics of reactor and comprise 3.1wt% hydrogenchloride and 2.3wt% carbon monoxide.
The IPDI that obtains from distillation process has the hydrolyzable cl content of 80ppm and the chloride content of 100ppm.
The IPDI of gained is further processed the formation tripolymer equally.In 70% solution in the commercial practices paint solvent, tripolymer is that in fact water is clear, has the gloomy chromatic number in Kazakhstan of 30Apha.
Embodiment 3 (comparative example)
By in slick injection nozzle, mixing, reactant stream A and reactant stream B are supplied to tubular reactor continuously, it has the post-processing stages of the isocyanic ester condensation phase in downstream and distillation isocyanic ester subsequently, reactant stream A is hexamethylene-diamine/noble gas mixtures, reactant stream B is that the amount of introducing is 220% of a theory by the phosgene of evaporation in the mono chloro benzene (reclaims excessive and from the condensation phosgene of the phosgene generation technology) phosgene that solution obtains.Phosgene reaction thing flow B comprise 6.9wt% hydrogenchloride and the 0.05wt% carbon monoxide.The temperature of two kinds of reactant streams is 300 ℃.The little normal atmosphere that is higher than of pressure in the tubular reactor is at 1400 millibars.
The about 50m/s of the speed of component A in smooth injection nozzle, the speed of B component is about 10m/s before mixing.Because the result of adiabatic reaction state, temperature of reactor rises to about 450 ℃.
After leaving reactor, hexamethylene diisocyanate (HDI) reaction product is condensed, and with hydrogen chloride by-product, inert substance separates with excess phosgene, then purifying in distillation process.The HDI that obtains has the hydrolyzable cl content of 50ppm and the chloride content of 430ppm.
The HDI of gained is further processed the formation tripolymer, has the very polyisocyanates of the trifunctional of low-steam pressure, and it is applied to the covering system.Tripolymer is that in fact water is clear, has the gloomy chromatic number in Kazakhstan of 80Apha.
Embodiment 4 (the present invention)
Similarity condition repeats down embodiment 3, phosgene reaction thing flow B still theoretical 220%, it is 120% that the phosgene solution by vaporization cycle is recycled to degree, the phosgene that reacts required directly provides from phosgene generation technology, comprises inert substance and carbon monoxide.Phosgene reaction thing flow B comprises 6.3wt% hydrogenchloride and 3.4wt% carbon monoxide.
The HDI that obtains from distillation process has the hydrolyzable cl content of 20ppm and the chloride content of 190ppm.
The HDI of gained is further processed the formation tripolymer equally.Tripolymer is that in fact water is clear, has the gloomy chromatic number in Kazakhstan of 20Apha.
Embodiment 5 (the present invention)
By in nozzle, mixing, reactant stream A and reactant stream B are supplied to tubular reactor, it has the post-processing stages of the isocyanic ester condensation phase in downstream and distillation isocyanic ester subsequently, reactant stream A is by gaseous state 2,4-and 2, the mixture that 6-tolylene diamine and rare gas element are formed, reactant stream B, phosgene, 75%, by evaporation phosgene solution (it is excessive to reclaim), phosgene with reaction needed, directly,, comprise inert substance and excessive carbon monoxide with gas form from phosgene generation technology.Gaseous phosgene logistics from phosgene generation technology comprises 5.0% carbon monoxide.
The a little higher than normal atmosphere of pressure in the tubular reactor is 1500 millibars.Because the result of adiabatic reaction state, the temperature in the reactor rises to about 450 ℃.
Reaction product, for by 2,4-and 2, the mixture that 6-tolylene diisocyanate (TDI) is formed is condensed after leaving reactor, and with byproduct hydrogen chloride, inert substance separates with excessive phosgene, follows purifying in distillation process.The TDI that obtains has the hydrolyzable cl content of 30ppm and the chloride content of 80ppm, has the gloomy chromatic number in Kazakhstan of 20Apha.
One of ordinary skill in the art will readily recognize that in not deviating from its broad sense inventive concept and can change above-mentioned embodiment.Therefore it being understood that the present invention is not limited to disclosed specific embodiments, but intention covers aim of the present invention and the interior variation of scope that limits as accessory claim.

Claims (20)

1. a method comprises: amine reactant is provided; With in reaction zone, make amine reactant and phosgene logistics reaction form the product comprise corresponding isocyanate; Wherein the phosgene logistics has 0.5wt% or more CO content.
2. according to the process of claim 1 wherein that the reaction of amine reactant and phosgene logistics makes gaseous state amine not contain drop, and in reaction zone the preheating temperature value of phosgene and amine more than dew point.
3. according to the process of claim 1 wherein that the phosgene logistics has 1wt% or more CO content.
4. according to the process of claim 1 wherein that the phosgene logistics has the CO content that is less than 8wt%.
5. according to the process of claim 1 wherein that the phosgene logistics has the CO content of 1-8wt%.
6. according to the process of claim 1 wherein that the phosgene logistics has the HCl content of 0.1-10wt%.
7. according to the process of claim 1 wherein that the reaction of amine reactant photoreactive gas logistics is to carry out in the presence of the inert media that comprises the component that one or more are selected from nitrogen, chlorobenzene, dichlorobenzene and its mixture.
8. according to the method for claim 5, wherein the reaction of amine reactant photoreactive gas logistics is to carry out in the presence of the inert media that comprises the component that one or more are selected from nitrogen, chlorobenzene, dichlorobenzene and its mixture.
9. according to the process of claim 1 wherein that the reaction of amine reactant photoreactive gas logistics carrying out under the 200-570 ℃ of temperature and under the absolute pressure 0.8-3 crust in reaction zone.
10. method according to Claim 8, wherein the reaction of amine reactant photoreactive gas logistics is being carried out under the 200-570 ℃ of temperature and under the absolute pressure 0.8-3 crust in reaction zone.
11. according to the method for claim 9, wherein the high 20-2000 millibar of pressure in one of amine reactant feeding line photoreactive gas logistics feeding line or the pressure ratio reaction zone among both and wherein the reaction zone downstream pressure than the low 10-500 millibar of the pressure in the reaction zone.
12. according to the process of claim 1 wherein that the logistics of amine reactant photoreactive gas independently has the linear rate of flow that enters and pass reaction zone of 1-100m/s separately, wherein the logistics of amine reactant photoreactive gas has the 0.01-15 mutual average contact time of second in reaction zone.
13. method according to claim 11, wherein the logistics of amine reactant photoreactive gas independently has the linear rate of flow that enters and pass reaction zone of 1-100m/s separately, and wherein the logistics of amine reactant photoreactive gas has the 0.01-15 mutual average contact time of second in reaction zone.
14. according to the process of claim 1 wherein that the reaction thermal insulation of amine reactant and phosgene logistics carries out.
15., make the aliphatic series or the cyclic aliphatic isocyanic ester that generate comprise the compound that is less than 200ppm with hydrolyzable chlorine according to the method for claim 1.
16., make the aromatic isocyanate that generates comprise the compound that is less than 100ppm with hydrolyzable chlorine according to the method for claim 1.
17. do not having under the situation of intermediate purification according to the process of claim 1 wherein, the phosgene logistics directly offered described method from phosgene generation technology.
18. according to the method for claim 17, wherein phosgene generation technology comprises the reaction of CO and chlorine, wherein CO is 2-20% with respect to the molar excess of chlorine.
19. according to the method for claim 17, further comprise and from the reaction of amine reactant photoreactive gas logistics, reclaim unreacted phosgene, before the phosgene logistics enters into reaction zone, mix phosgene that reclaims and the phosgene that directly provides from phosgene generation technology.
20. according to the method for claim 18, further comprise and from the reaction of amine reactant photoreactive gas logistics, reclaim unreacted phosgene, before the phosgene logistics enters into reaction zone, mix phosgene that reclaims and the phosgene that directly provides from phosgene generation technology.
CNA2008101611558A 2007-08-22 2008-08-22 Process for preparing low-chlorine isocyanate Pending CN101372464A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103796991A (en) * 2011-03-31 2014-05-14 巴斯夫欧洲公司 Method for producing isocyanates
CN109312050A (en) * 2016-06-17 2019-02-05 科思创德国股份有限公司 The PUR/PIR hard foam for preparing the method for the composition containing isocyanate groups and isocyanurate group and being produced from it
CN109761855A (en) * 2018-12-20 2019-05-17 万华化学集团股份有限公司 A method of preparing isophorone diisocyanate
CN110396057A (en) * 2019-07-16 2019-11-01 万华化学（宁波）有限公司 A method of preparing the isocyanates of low chlorine content
CN111718282A (en) * 2020-06-30 2020-09-29 万华化学集团股份有限公司 Method for preparing isocyanate with low chlorinated impurity content based on salification phosgenation
WO2020252807A1 (en) * 2019-06-21 2020-12-24 万华化学集团股份有限公司 Polyisocyanate composition, preparation method therefor and use thereof
CN112824376A (en) * 2019-11-21 2021-05-21 万华化学集团股份有限公司 Method for preparing isocyanate with low hydrolytic chlorine content by gas phase method
CN116239501A (en) * 2022-12-14 2023-06-09 上海奕朗化工有限公司 Method for preparing low-chlorine 1, 5-pentanediisocyanate by high-temperature gas phase

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FR2965490B1 (en) 2010-09-30 2013-01-11 Aet Group DEVICE AND METHOD FOR CONTINUOUS PHOSGENATION
HUE034207T2 (en) * 2013-02-08 2018-01-29 Covestro Deutschland Ag Method for the separation of an isocyanate produced by phosgenation of a primary amine in the gas phase from the gaseous raw product of the phosgenation
JP2015010183A (en) * 2013-06-28 2015-01-19 旭化成ケミカルズ株式会社 Diisocyanate composition
JP6562521B2 (en) 2017-09-29 2019-08-21 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ Optical member resin manufacturing method, optical member resin, spectacle lens, and spectacles
CN112142623A (en) * 2019-06-27 2020-12-29 万华化学（宁波）有限公司 Preparation method and application of low-activity MDI-50 product

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Cited By (13)

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Publication number Priority date Publication date Assignee Title
CN103796991A (en) * 2011-03-31 2014-05-14 巴斯夫欧洲公司 Method for producing isocyanates
CN103796991B (en) * 2011-03-31 2016-05-18 巴斯夫欧洲公司 Prepare the method for isocyanates
CN109312050A (en) * 2016-06-17 2019-02-05 科思创德国股份有限公司 The PUR/PIR hard foam for preparing the method for the composition containing isocyanate groups and isocyanurate group and being produced from it
CN109761855A (en) * 2018-12-20 2019-05-17 万华化学集团股份有限公司 A method of preparing isophorone diisocyanate
US11939280B2 (en) 2018-12-20 2024-03-26 Wanhua Chemical Group Co., Ltd. Method for preparing isophorone diisocyanate
WO2020252807A1 (en) * 2019-06-21 2020-12-24 万华化学集团股份有限公司 Polyisocyanate composition, preparation method therefor and use thereof
CN110396057B (en) * 2019-07-16 2022-02-18 万华化学集团股份有限公司 Method for preparing isocyanate with low chlorine content
CN110396057A (en) * 2019-07-16 2019-11-01 万华化学（宁波）有限公司 A method of preparing the isocyanates of low chlorine content
CN112824376A (en) * 2019-11-21 2021-05-21 万华化学集团股份有限公司 Method for preparing isocyanate with low hydrolytic chlorine content by gas phase method
CN112824376B (en) * 2019-11-21 2023-01-13 万华化学集团股份有限公司 Method for preparing isocyanate with low hydrolytic chlorine content by gas phase method
CN111718282A (en) * 2020-06-30 2020-09-29 万华化学集团股份有限公司 Method for preparing isocyanate with low chlorinated impurity content based on salification phosgenation
CN111718282B (en) * 2020-06-30 2022-08-05 万华化学集团股份有限公司 Method for preparing isocyanate with low chlorinated impurity content based on salification phosgenation
CN116239501A (en) * 2022-12-14 2023-06-09 上海奕朗化工有限公司 Method for preparing low-chlorine 1, 5-pentanediisocyanate by high-temperature gas phase

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